JP2009221242A - Flame-retardant polyester resin composition and fiber structure comprised of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin composition that is suppressed in drip on combustion, has a flame retardant highly dispersed therein and exhibits high flame-retardant performances, and a fiber structure. <P>SOLUTION: The flame-retardant polyester resin composition comprises, at least, 5-30 wt.% of polyphenylene ether having a molecular weight of 500-10,000 and 0.5-20 wt.% of polyorganosiloxane. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a flame retardant polyester resin composition having high flame retardancy and high dispersibility of a flame retardant, and a fiber comprising the flame retardant because of the synergistic effect of specific polyphenylene ether and organopolysiloxane resin. It relates to structures.

  Conventionally, halogen flame retardants such as chlorine-containing flame retardants and bromine-containing flame retardants, or halogen flame retardants and antimony flame retardants have been used as flame retardant methods for materials such as flammable resins and flammable fibers. Many materials have been proposed. However, although these materials are excellent in flame retardancy, halogen flame retardants have problems such as the possibility of generating halogenated gas during combustion, and many studies have been made to solve these problems. .

  For example, studies have been made using phosphorus compounds as flame retardants that do not contain halogen elements or antimony elements. Many materials containing phosphoric flame retardants using phosphate esters have been proposed, but the flame retardancy is lower than that of halogen and antimony flame retardants, and the flame retardant performance is insufficient. There was a problem to do.

On the other hand, studies using silicone compounds as flame retardants have been conducted. This silicone compound is monofunctional R ₃ SiO _0.5 (M unit), bifunctional R ₂ SiO _1.0 (D unit), trifunctional RSiO _1.5 (T unit), 4 It is comprised from either of the structural units shown by functional _SiO2.0 (Q unit). It has been proposed that excellent flame retardancy is exhibited by using a specific compound having a unit represented by RSiO _1.5 (see, for example, Patent Document 1). However, this proposal can exhibit excellent flame retardancy without using a halogen-based flame retardant, but there is a problem that it is not sufficient when higher flame retardancy is required.

  In addition, it has been proposed to use a polyphenylene ether resin as a highly flame-retardant resin composition (see, for example, Patent Document 2). This high molecular weight polyphenylene ether has a low dispersibility in polyester, and there is a problem that a molded product having sufficient physical properties cannot be obtained when molding such as fiberization. Therefore, in order to improve the dispersibility, it is necessary to use a modified polyphenylene ether mixed with polystyrene having compatibility with polyphenylene ether or a compatible solvent, and therefore there is a problem that it is not sufficient in terms of flame retardancy.

That is, the present situation is that there is nothing sufficient in terms of flame retardancy of the polyester resin composition and fiber and dispersibility of the flame retardant.
JP 2006-233186 A Japanese Patent Laid-Open No. 2000-212411

  An object of the present invention is to provide a polyester resin composition and a fiber structure in which the drip at the time of combustion is suppressed, the dispersibility of the flame retardant is high, and the flame retardancy is high.

In order to solve the above problems, the present invention has the following configuration. That is,
(1) A flame retardant polyester resin composition comprising at least 5 to 30% by weight of polyphenylene ether having a molecular weight of 500 to 10,000 and 0.5 to 20% by weight of polyorganosiloxane.

(2) The flame retardant polyester resin composition as described in (1) above, wherein the polyorganosiloxane is represented by the following general formula.
(C ₆ H ₅ ) _m1 R _m2 SiX _n O _{(4-m1-m2-n) / 2} (1)
[In the formula, R is a monovalent organic group excluding a hydrogen atom or a phenyl group, X is an OH group or a hydrolyzable group, and m1, m2, and n are
0.3 ≦ m1 ≦ 1.8,
0 ≦ m2 ≦ 1.5,
1.0 ≦ m1 + m2 <2.0,
0.2 ≦ m1 / (m1 + m2) ≦ 1.0,
0 ≦ n ≦ 1.5
A number satisfying the range of
1.0 ≦ m1 + m2 + n ≦ 3.0
It is a number that satisfies
(3) The flame-retardant polyester according to (1) or (2) above, containing 0.01 to 3% by weight of an organic alkali metal sulfonate and / or an organic alkaline earth metal sulfonate Resin composition.

  (4) The flame retardant polyester resin composition as described in any one of (1) to (3) above, which contains 1 to 15% by weight of a boric acid metal salt.

  (5) A fiber structure comprising the flame retardant polyester resin composition according to any one of (1) to (4).

  According to the present invention, as a flame retardant resin material or a flame retardant fiber material, specifically, in industrial use, clothing use, non-clothing use, etc., it has high flame retardancy, excellent drip suppression effect, and production. A highly stable flame-retardant polyester resin composition and fiber structure can be provided.

  Hereinafter, the flame-retardant polyester resin composition of the present invention will be described in detail.

  The polyester resin composition of the present invention is a flame retardant polyester resin composition comprising at least 5 to 30% by weight of polyphenylene ether having a molecular weight of 500 to 10,000 and 0.5 to 20% by weight of polyorganosiloxane. . High flame retardancy is achieved by the synergistic effect of polyphenylene ether and polyorganosiloxane.

  As the polyester resin in the present invention, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polylactic acid, polybutylene succinate and the like can be preferably used, but polyethylene terephthalate is preferable.

  The polyethylene terephthalate in the present invention preferably contains 80 mol% or more of ethylene terephthalate units. This is because fibers having excellent mechanical properties can be obtained when the resin is used for fibers. More preferably, it is 90 mol% or more, and more preferably 95 mol% or more.

  In the present invention, the polyester resin can be copolymerized as long as the ethylene terephthalate unit satisfies the above range. As copolymerization components, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl Aliphatic dihydroxy compounds such as glycol, polyoxyalkylene glycols such as diethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, alicyclic dihydroxy compounds such as 1,4-cyclohexanedimethanol, fragrances such as bisphenol A and bisphenol S Group dihydroxy compounds and the like. Preferred dicarboxylic acid components include 2,6-naphthalenedicarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, isophthalic acid having a sulfonic acid metal base, and aromatic such as phthalic acid. Dicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, aliphatic dicarboxylic acid such as fumaric acid, alicyclic dicarboxylic acid such as 1,4-cyclohexanedicarboxylic acid, paraoxybenzoic acid, etc. An oxycarboxylic acid etc. can be mentioned. Examples of the dicarboxylic acid ester derivatives include esterified products of the above dicarboxylic acid compounds, such as dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethyl methyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, and adipic acid. Examples thereof include dimethyl, diethyl maleate and dimethyl dimer.

  Among these, as the dicarboxylic acid compound, isophthalic acid having a sulfonic acid metal base or a dimethyl ester derivative thereof can be preferably used. As the glycol compound, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol and bisphenol A can be preferably used as a copolymerization component.

  It is important that the polyester resin in the flame-retardant polyester resin composition of the present invention is 40 to 90% by weight. When it is 40% by weight or more, a fiber having excellent mechanical properties derived from polyester can be obtained when the resin is used for fibers. Moreover, the flame-retardant performance outstanding with the flame retardant used for others is acquired by setting it as 90 weight% or less. 50 weight% or more is preferable and 65 weight% or more is more preferable. 80 weight% or less is preferable and 75 weight% or less is more preferable.

  The flame retardant polyester resin composition in the present invention contains polyphenylene ether having a molecular weight of 500 to 10,000.

  The polyphenylene ether in the present invention is a compound having the structure of the following general formula (2).

R ₁ to R ₄ each represent the same or different substituent, and each represents hydrogen, an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an aryl group, a substituted aryl group, an alkoxy group, or a substituted alkoxy group.

  X represents a disubstituted aliphatic hydrocarbon residue and a substituted derivative thereof, hydrogen, sulfur, or a sulfonyl group.

X and OR ₅ can be in the ortho and para positions. From the viewpoint of flame retardancy, it is preferable that both take the ortho position. R ₁ to R ₄ preferably take the para position of X, but are not limited thereto.

In the polyphenylene ether of the present invention, R ₁ to R ₄ are all methyl groups, X is isopropylidene, R ₁ to R ₄ are all methyl groups, X is methylene, and R ₁ to R ₄ are all methyl groups. A compound in which X is cyclohexylidene is preferably used.

R ₅ may be H, a glycidyl group, or a styryl group. A glycidyl group is more preferable from the viewpoint of flame retardancy. In the present invention, m and n are each an integer of 0 or more, and m + n is preferably 4 to 80.

  The molecular weight of the polyphenylene ether in the present invention is 500 to 10,000. When the molecular weight is 500 or more, flame retardancy is improved. When the molecular weight is 10,000 or less, the dispersibility of polyphenylene ether in the polyester resin is improved. 8000 or less is preferable and 5000 or less is more preferable. Moreover, 1000 or more are preferable and 2000 or more are preferable.

  In the present invention, 5 to 30% by weight of polyphenylene ether is used. Use of 5% by weight or more improves flame retardancy, and use of 30% by weight or less improves the physical properties of the obtained polymer. 10 weight% or more is preferable and 20 weight% or less is preferable. More preferably, it is 15% by weight or less.

  The method for producing the polyphenylene ether of the present invention is performed based on a known method. For example, a precipitation polymerization method in which a poor solvent of polyphenylene ether is used as a polymerization solvent and polyphenylene ether is precipitated as particles as the polymerization proceeds, and a solution in which polyphenylene ether is dissolved in the solvent using a good solvent as the polymerization solvent Although a polymerization method is known, the low molecular weight polyphenylene ether of the present invention can be obtained by either method.

  When a precipitation polymerization method, that is, a precipitation polymerization method in which a polyphenylene ether poor solvent is used as a polymerization solvent and polyphenylene ether is precipitated as the polymerization proceeds, it is preferable to use a combination of a poor solvent and a good solvent. As the poor solvent, alcohol having 1 to 10 carbon atoms is preferable, and methanol, ethanol, propanol, butanol, pentanol, hexanol, and ethylene glycol can be exemplified. A combination of a plurality of alcohols is also optional. It is preferable that this poor solvent does not contain water. The good solvent is used as long as the low molecular weight polyphenylene ether is not dissolved.

  On the other hand, it is also possible to use a solution polymerization method in which a good solvent of polyphenylene ether is used as a polymerization solvent and a poor solvent is added to the resulting solution containing low molecular weight polyphenylene ether to precipitate low molecular weight polyphenylene ether.

  Good solvents include benzene, toluene, xylene (including o-, m-, and p-isomers), ethylbenzene, aromatic hydrocarbons such as styrene, chloroform, methylene chloride, 1,2-dichloroethane, chlorobenzene, di- Examples thereof include halogenated hydrocarbons such as chlorobenzene and nitro compounds such as nitrobenzene. A preferred good solvent is toluene. The concentration of the low molecular weight polyphenylene ether in the solution is not particularly limited, but is preferably 25 to 70% by weight. The polymerization solution can be used as a raw material for the coating as it is, but a precipitation operation is required to obtain a solvent-based coating different from that used in the polymerization.

  The low molecular weight polyphenylene ether is precipitated by a method in which a solution containing a low molecular weight polyphenylene ether and a poor solvent are continuously added to a suitably sized tank having a stirrer, and a tank containing a solution containing a low molecular weight polyphenylene ether is poor. Examples include a method of adding a solvent, a method of adding a low molecular weight polyphenylene ether solution to a tank containing a poor solvent, and a method of continuously adding a low molecular weight polyphenylene ether solution and a poor solvent to a tubular static mixer. it can. Examples of the poor solvent include ethers, ketones, and alcohols. Preferably it is C1-C10 alcohol, More preferably, it is at least 1 sort (s) chosen from methanol, ethanol, propanol, butanol, pentanol, hexanol, and ethylene glycol. These may contain water. The precipitation temperature is preferably -80 to + 20 ° C.

In addition, when R ₅ in the general formula (2) is not H but a glycidyl group or a styrene group is employed, the method for imparting the functional group to the terminal of the polyphenylene ether is not limited. The end groups may be reacted simultaneously when polymerizing the polyphenylene ether, or the reaction may be carried out in a solution system or a melt system once the polyphenylene ether is obtained.

  Examples of monomers used for the production of polyphenylene ether include, for example, o-cresol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2, 6-diethylphenol, 2-n-propylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2-phenylphenol, 2,6-diphenylphenol Nord, 2,6-bis - (4-fluorophenyl) phenol, 2-methyl-6-tolyl phenols, such as 2,6-di-tolyl phenols. These compounds may be used alone or in combination of two or more. Moreover, even if it contains a small amount of m-cresol, p-cresol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, etc., it does not matter. Among these, 2,6-dimethylphenol is industrially important. A combination of 2,6-dimethylphenol and 2,3,6-trimethylphenol or a combination of 2,6-dimethylphenol and 2,6-diphenylphenol is also preferably used.

  In the present invention, it is preferable that the weight loss rate of polyphenylene ether at 300 ° C. is 5% by weight or less. The weight loss rate at 300 ° C. is the ratio of the weight loss rate at 300 ° C. when a sample from which moisture adhering to the compound is removed is heated from room temperature at a rate of 10 ° C./min in a nitrogen atmosphere. And can be measured with a differential thermothermal gravimetric simultaneous measurement device (TG-DTA) or the like. This is because, when the weight loss ratio at 300 ° C. is 5% by weight or less, the physical properties can be suppressed from decreasing in the molding of the polyester resin of the present invention. The heat loss rate at 300 ° C. is preferably 3% by weight or less, and more preferably 0.5% by weight or less.

  In this invention, it is preferable that an organic alkali metal salt is included. This is because the flame retardant performance is improved by a synergistic effect with polyphenylene ether. The organic alkali metal salt is preferably an alkali metal salt of perfluoroalkanesulfonic acid and aromatic sulfonic acid, specifically, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfonimide, diphenylsulfone- Examples include potassium 3-sulfonate, potassium perfluorobutanesulfonate, and sodium p-toluenesulfonate. It is more preferable that one or more selected from these.

  The added amount of the organic alkali metal salt is preferably 0.01 to 3% by weight. This is because the flame retardant effect of the organic alkali metal salt is manifested at 0.01% by weight or more, and by making it 3% by weight or less, thermal decomposition during the molding of polyethylene terephthalate can be suppressed. 0.1% by weight or more is preferable, and 2% by weight or less is preferable. 1% by weight or less is more preferable.

  The polyester resin composition of the present invention contains 0.5 to 20% by weight of polyorganosiloxane. This is because high flame retardancy is exhibited by the synergistic effect of polyorganosiloxane and polyphenylene ether.

  By containing polyorganosiloxane in an amount of 0.5% by weight or more, a sufficient flame retardant effect is exhibited, and by making it 20% by weight or less, the fiber characteristics when resin or fiberized is improved. The amount added is preferably 5% by weight or more, and more preferably 10% by weight or less.

The polyorganosiloxane in the present invention refers to a silicone compound containing a unit represented by R ″ SiO _1.5 . The organic group R ″ of the polyorganosiloxane contains a phenyl group, and the content of the phenyl group is a polyorgano. It is preferable that it is 30% or more by molar ratio with respect to all the organic groups which comprise siloxane. This is because when the phenyl group content is 30 mol% or more, the heat resistance of the polyorganosiloxane is improved, and thus the flame retardancy of the polyester resin composition of the present invention and the fiber structure comprising the polyester resin composition is improved. . The content of the phenyl group is preferably 50 mol% or more, and more preferably 90 mol% or more.

It is preferable that the organopolysiloxane satisfies the following general formula (1).
(C ₆ H ₅ ) _m1 R _m2 SiX _n O _{(4-m1-m2-n) / 2} (1)
[In the formula, R is a monovalent organic group excluding a hydrogen atom or a phenyl group, X is an OH group or a hydrolyzable group, and m1, m2, and n are
0.3 ≦ m1 ≦ 1.8,
0 ≦ m2 ≦ 1.5,
1.0 ≦ m1 + m2 <2.0,
0.2 ≦ m1 / (m1 + m2) ≦ 1.0,
0 ≦ n ≦ 1.5
A number satisfying the range of
1.0 ≦ m1 + m2 + n ≦ 3.0
It is a number that satisfies
By selecting the organopolysiloxane of the general formula (1), it is possible to give excellent flame retardancy and drip suppression to the polyester resin due to a synergistic effect with the specific polyphenylene ether.

  R is a monovalent organic group excluding a hydrogen atom or phenyl group, preferably a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and having 1 to 8 carbon atoms. Are preferably an alkyl group, an aralkyl group, a cycloalkyl group, a halogen-substituted alkyl group, and the like. In particular, a methyl group is preferred industrially.

The functional group X is a hydrolyzable group (—OR ′) in which a silanol group (—OH) or a hydrogen atom of the silanol group (—OH) is substituted with a predetermined functional group R ′. Is a functional group that is essential for improving the flame retardancy, drip suppression effect and production stability of the polyester resin composition according to the present invention. When a functional group having no hydrolyzability such as trimethylsiloxy group (—OSi (CH ₃ ) ₃ ) is selected instead of the functional group (—OR ′), a polyester resin composition containing the organopolysiloxane The flame retardancy of objects may be reduced and drip may occur during combustion.

  From the viewpoint of production stability, the ratio of hydrolyzable groups (—OR ′) in which the hydrogen atom of the silanol group (—OH) in the functional group X is substituted with a predetermined functional group R ′ is 0.5 or more. Preferably, 0.8 or more is more preferable, and 0.9 or more is more preferable.

  The functional group R ′ is preferably one or more groups selected from linear alkyl groups having 8 to 21 carbon atoms or aryl groups. When these functional groups are used, the increase in the molecular weight of the organopolysiloxane and the effect of suppressing the disappearance of the glass transition point are great even at high temperatures, and the flame retardancy of the polyester resin composition containing the organopolysiloxane is improved. Drip is suppressed.

  Specific examples of the alkyl group of the functional group R ′ include n-octyl group, 2 octyl group, nonyl group, 2-nonyl group, 3-nonyl group, 4-nonyl group, 5-nonyl group, 3, 5, 5 -Trimethyl-1-hexyl group, decyl group, isodecyl group, undecyl group, 2-undecyl group, dodecyl group, 2-dodecyl group and the like can be mentioned. Specific examples of R ′ which is an aryl group include phenyl group, o-hydroxyphenyl group, m-hydroxyphenyl group, p-hydroxyphenyl group, 2,3,5-trimethylphenyl group, 2-vinylphenyl group, 4- Vinylphenyl group, 2-ethylphenyl group, 4-ethylphenyl group, 2-allylphenyl group, 2-n-propylphenyl group, 2-isopropylphenyl group, 2-isopropyl-5-methylphenyl group, 3-methyl- 4-isopropylphenyl group, 4-n-butylphenyl group, 2-s-butylphenyl group, 4-s-butylphenyl group, 3-t-butylphenyl group, 4-t-butylphenyl group, 2,6- Di-s-butylphenyl group, 2,4-di-t-butylphenyl group, 2,6-di-t-butylphenyl group, 2,4,6-tri-t-butyl Enyl group, 4-n-pentylphenyl group, 4-t-pentylphenyl group, 2,4-di-t-pentylphenyl group, 4-n-hexylphenyl group, 4-n-heptylphenyl group, 2,6 -Di-t-butyl-4-methylphenyl group, 2,4-di-t-butyl-5-methylphenyl group, 2,4,6-tri-t-butylphenyl group, 4-n-octylphenyl group 4-t-octylphenyl group, 4-nonylphenyl group, 2,4-di-nonylphenyl group, 4-dodecylphenyl group, 2-phenylphenyl group, 4-phenylphenyl group, 4-α-cumylphenyl group, Examples include 2,4,6-tri (α-methylbenzyl) phenol 1-naphthyl group, α-naphthyl group, β-naphthyl group, and the like. Among them, flame retardancy, drip suppression, melt molding of polyester resin containing organopolysiloxane from which p-phenylphenyl group, p-α-cumylphenyl group, 3-methyl-4-isopropylphenyl group and octyl group are obtained Good and preferable.

  The organopolysiloxane represented by the general formula (1) preferably has a weight average molecular weight Mw in the range of 1500 to 10,000, and more preferably in the range of 2000 to 7500. The weight average molecular weight is measured by gel permeation chromatography (GPC) and is determined in terms of polystyrene. When the weight average molecular weight of the organopolysiloxane is in the above range, the organopolysiloxane is softened with an appropriate melt viscosity, so that it does not become a foreign matter and has good dispersibility, and exhibits good processability of the polyester resin composition. be able to. In addition, when the weight average molecular weight of the organopolysiloxane is in the range of 2,000 or more and 5,000 or less, the flame retardancy of the resulting polyester resin composition is improved, from the viewpoint of suppression of drip and processability (production stability). Is particularly preferred.

  On the other hand, when the weight average molecular weight of the organopolysiloxane exceeds 7500, the viscosity of the organopolysiloxane is high during melt-kneading, the dispersibility of the organopolysiloxane is deteriorated, and the softening point of the organopolysiloxane disappears. This is not preferable because the formation of foreign matter occurs and the workability deteriorates. Further, when the weight average molecular weight of the organopolysiloxane is less than 2000, the melt viscosity of the organopolysiloxane is lowered, the dispersibility is deteriorated, and the processability of the polyester resin composition containing the organopolysiloxane is deteriorated. is there.

  The glass transition point of the organopolysiloxane is preferably 70 ° C. or higher and 290 ° C. or lower because the moldability of the polyester resin composition is improved. If the glass transition point of the organopolysiloxane exceeds 290 ° C., the organopolysiloxane does not soften during the molding process and becomes a foreign substance, which is not preferable. From the viewpoint of molding processability, a more preferable range of the glass transition point is 80 ° C. or higher and 200 ° C. or lower, and more preferably 100 ° C. or higher and 150 ° C. or lower.

  In the polyester resin composition containing the organopolysiloxane according to the present invention, the resin is prevented from changing over time to deteriorate the flame retardancy, the drip suppression effect, and the production stability. In addition, since the organopolysiloxane according to the present invention does not easily undergo a condensation reaction of the organopolysiloxane resin due to heat received during production or the like, an increase in molecular weight is suppressed and a softening point is maintained. For this reason, the polyester resin composition containing the organopolysiloxane according to the present invention can be easily produced without causing an increase in filtration pressure or poor dispersion due to filter clogging during processing using a twin-screw kneader or a spinning machine. This has the advantage of being excellent in productivity.

  The method for producing the organopolysiloxane is not particularly limited. For example, organosilanes having at least one phenyl group selected from the group consisting of phenylchlorosilanes and phenylalkoxysilanes according to the molecular structure and molecular weight of the target organopolysiloxane, and optionally other organochlorosilanes After reacting with appropriate water, if necessary, the molecular weight is further increased using a condensation reaction accelerating catalyst, and silanol groups (-OH) are removed by removing the added organic solvent, by-product hydrochloric acid and low-boiling compounds. ) -Containing organopolysiloxane can be obtained. Further, by adding an alcohol compound or a phenol compound and reacting with part or all of the silanol group (—OH) in the organopolysiloxane, the hydrogen atom of the silanol group is substituted in the organopolysiloxane. Thus, an organopolysiloxane having an alkoxy group can be produced.

  Specific examples of phenylchlorosilanes include phenyltrichlorosilane, diphenyldichlorosilane, triphenylchlorosilane, and phenylmethyldichlorosilane.

  Specific examples of phenylalkoxysilanes include phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, phenylmethyldimethoxysilane, and phenylmethyldiethoxysilane. Illustrated.

  Specific examples of other organochlorosilanes include alkylchlorosilanes such as tetrachlorosilane, methyltrichlorosilane, dimethyldichlorosilane, and trimethylchlorosilane; fluorinated alkylchlorosilanes such as trifluoropropyltrichlorosilane and trifluoropropylmethyldichlorosilane; tetramethoxysilane , Tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, and other alkyl alkoxysilanes; trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane , Trifluoropropylmethyldimethoxysilane, trifluoropropylmethyldiethoxy Fluorinated alkyl alkoxy silanes, such as run is illustrated.

  Among these, from the viewpoint of flame retardancy, the organochlorosilane is a mixture of phenylchlorosilane and alkylchlorosilane in a ratio (molar ratio) of 100/0 to 1/99, and the organoalkoxysilane comprises phenylalkoxysilane and alkylalkoxysilane. It is preferable that they are mixed at a ratio of 100/0 to 1/99. Here, phenylchlorosilane, alkylchlorosilane, phenylalkoxysilane and alkylalkoxysilane are exemplified by the silanes exemplified above. More preferably, the organochlorosilane has a mixing ratio of phenylchlorosilane and alkylchlorochlorosilane or a mixing ratio of phenylalkoxysilane and alkylalkoxysilane of 100/0 to 50/50, and difficult to be 100/0 to 90/10. Particularly preferred from the standpoint of flammability.

  A known condensation catalyst can be used as the condensation reaction promoting catalyst for preparing the organopolysiloxane raw material. Specific examples include organic acid tin salts, organic acid titanium salts, organic acid zirconium salts, organic acid metal salts such as organic acid aluminum salts, and phosphorus compounds that are phosphine oxides. In particular, phosphorus compounds such as phosphine oxide are preferable.

  The temperature and time of the hydrolysis-condensation reaction or condensation reaction may vary depending on the reactivity of the raw materials and the implementation scale, but it is usually possible to select a reaction time of 1 to 29 hours at a temperature of 10 to 150 ° C. it can.

  The organic solvent used for the hydrolysis condensation reaction or the condensation reaction is an aromatic hydrocarbon such as toluene or xylene, an aliphatic hydrocarbon such as hexane or octane, an alcohol such as methanol, ethanol or 2-propanol, or acetone. It can be selected from solvents such as ketones such as methyl ethyl ketone.

  In this invention, it is preferable to contain a boric acid metal salt. The boric acid metal salt is not particularly limited, but it is preferable to use a borate such as zinc borate and magnesium borate. Borate exhibits high flame retardancy by interaction with polyorganosiloxane.

  The boric acid metal salt is preferably contained in an amount of 1 to 15% by weight. When the content is 1% by weight or more, flame retardancy can be expressed, and when the content is 15% by weight or less, the dispersibility of the flame retardant is improved. It is preferably 3% by weight or more, and preferably 10% by weight or less. More preferably, it is 5 weight% or less.

  In the present invention, flame retardants other than those described above can be used. In this invention, it can select from the compound generally used as a flame retardant. Specific examples include hydrated metal flame retardants such as magnesium hydroxide, layered silicates such as montmorillonite, phosphorus compounds such as phosphinates, diphosphinates, polyphosphates, ammonium polyphosphates, and melamine derivatives. And nitrogen-containing compounds.

  In the composition of the present invention, various additives other than the flame retardant can be appropriately blended depending on the purpose within a range not impairing the characteristics. Examples of additives include antioxidants, ultraviolet absorbers, stabilizers, light stabilizers, compatibilizers, other types of non-halogen flame retardants, lubricants, fillers, adhesion aids, and rust inhibitors.

  Antioxidants usable in the present invention include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl). ) Propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4 , 4′-butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8 10-tetraoxaspiro [5,5] undecane, 4,4-thiobis- (2-tert-butyl-5-methylphenol), 2,2-methylenebis- (6-tert-butyl-methylphenol), 4, 4-methylenebis- (2,6-di-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris Nonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol phosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) Nyl) octyl phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-di-phosphonite, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′- Thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), 2,5,7,8-tetramethyl-2 (4,8,12-trimethyldecyl) chroman-2-ol, 5,7- Di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 , 6-Dipentylphenyl acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate , Tetrakis (methylene) -3- (dodecylthiopropionate) methane and the like.

  Stabilizers that can be used in the present invention include lithium stearate, magnesium stearate, calcium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc laurate, zinc ricinoleate, stearin Various metal soap stabilizers such as zinc acid, various organic tin stabilizers such as laurate, malate and mercapto, various lead stabilizers such as lead stearate and tribasic lead sulfate, and epoxy compounds such as epoxidized vegetable oil Phosphite compounds such as alkylallyl phosphite and trialkyl phosphite, β-diketone compounds such as dibenzoylmethane and dehydroacetic acid, hydrotalcites and zeolites.

  Examples of light stabilizers that can be used in the present invention include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxalic anilide-based UV absorbers, hindered amine-based light stabilizers. Agents and the like.

  Examples of the compatibilizer that can be used in the present invention include acrylic organopolysiloxane copolymers, partially crosslinked products of silica and organopolysiloxane, silicone powder, anhydrous maleated graft-modified polyolefin, carboxylated graft-modified polyolefin, polyolefin graft-modified organo Examples include polysiloxane.

  Examples of the adhesion assistant that can be used in the present invention include various alkoxysilanes.

  In the present invention, a hindered phenol stabilizer can be added as necessary. The addition amount of the hindered phenol stabilizer in that case is 0.01-3 weight% with respect to a polyester resin composition, Preferably it can add at 0.01-1 weight%.

  In the present invention, a small amount of a thermoplastic resin, for example, an olefin polymer such as polycarbonate, polyamide, polyphenylene oxide, polypropylene, polyethylene, ethylene / propylene copolymer, ethylene / 1-, as long as the object of the present invention is not impaired. Olefins such as butene copolymers, ethylene / propylene / non-conjugated diene copolymers, ethylene / ethyl acrylate copolymers, ethylene / glycidyl methacrylate copolymers, and ethylene / propylene-g-maleic anhydride copolymers Copolymers, polyether ester elastomers, polyester elastomers and the like can also be added.

  Next, the manufacturing method of the polyester resin composition of this invention is demonstrated.

  The polyester resin composition of the present invention contains at least the aforementioned organopolysiloxane and specific polyphenylene ether, and can be added to the polyester fat composition by a known method. For example, a method of mixing a polyester resin and various additives using a twin screw extruder, a Banbury mixer, or the like can be mentioned. However, the method is not limited to this as long as it can be mixed and dispersed in a thermoplastic resin.

  Next, the fiber structure comprising the polyester resin composition of the present invention will be described.

  The fiber structure referred to in the present invention is a fiber produced from a polyester resin composition, such as monofilament, multifilament, staple fiber, nanofiber, tow, high bulk suf, high bulk tow, spun yarn, blended yarn, processed yarn, false twisted yarn, Includes irregular shaped yarn, hollow yarn, conjugated yarn, partially oriented yarn, drawn yarn, sliver and the like. Moreover, the thing generally recognized as fiber bodies, such as a woven fabric, a knitted fabric, a nonwoven fabric, a string, a rope, felt, paper, a net | network, containing the fiber manufactured from the said polyester resin composition is included.

  It is preferable to contain 70% or more of the above-mentioned polyester resin composition by weight ratio with respect to the fiber structure, but this is not the only case. The effect of suppressing drip, flame retardancy, physical property deterioration of resin composition and processing characteristics It is possible to blend with other fibers or blend in a range where there is no decrease in the fiber.

Further, the fiber structure of the present invention can be suitably used as a filament or a staple. For example, as a filament for clothing, the single yarn fineness is in the range of 0.1 dtex to several tens dtex, and the total fineness is from 50 dtex. The number of filaments is preferably in the range of 10 to 100 at 300 dtex. In addition, the filaments obtained in this way can be obtained as a fiber structure by weaving into a woven fabric such as a triple structure, a change structure, or a double structure, a double structure or a vertical structure, such as a single structure. Can do. Moreover, it is preferable that the mass of the fiber structure at this time is in the range of 50 g / m ² or more and 500 g / m ² or less.

Further, for example, the filament for industrial use has a single yarn fineness in the range of several tens of Dtex to several hundred Dtex, and the total fineness in the range of several hundred Dtex to several thousand Dtex, and the number of filaments ranges from 10 to 100. In addition, the filament obtained in this way is woven into a woven fabric such as a triple structure or a change structure, which is a single structure, a double structure or a vertical structure, such as a single structure, as in clothing applications. It can be obtained as a structure. Further, it is preferable that the mass in the range of 300 g / ^{m 2} or more 1500 g / ^{m 2} or less of the fiber structure in this case.

  Thus, the fiber comprising the polyester resin composition of the present invention can be obtained in the form of a fabric such as a woven fabric, a knitted fabric, or a non-woven fabric, and as a textile product, a textile product that particularly requires a drip suppression effect and flame retardancy, For example, it can be suitably used as a textile product in which drip is suppressed and flame retardancy is exhibited by vehicle interior materials such as car seats and car mats, interior materials such as curtains, carpets and chair upholstery, and clothing materials.

Hereinafter, the present invention will be described in more detail with reference to examples. Each characteristic value in the examples is obtained by the following method.
A. Weight average molecular weight (organopolysiloxane)
Evaluation was made based on the weight average molecular weight in terms of standard polystyrene determined by average molecular weight gel permeation chromatography using the following analyzer.

Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSKgelG1000HHR (manufactured by Tosoh Corporation)
Measurement temperature: 40 ° C. (column oven temperature)
Flow rate: 1 ml / min Chloroform sample: Use organopolysiloxane as 1% chloroform solution Measurement of glass transition point The glass transition point was measured by the following analyzer.

Apparatus: DSC2920 Modulated DSC (manufactured by TA Instruments)
Temperature rising rate: 2 ° C./min ¹ H NMR, ²⁹ Si NMR
Using JNM-EX400 (manufactured by JEOL Ltd.), ¹ H-nucleus and ²⁹ Si-nuclear magnetic resonance spectrum analysis was performed using deuterated chloroform as a solvent, and the amount of silanol groups of the organopolysiloxane was calculated.
D. Number average molecular weight (polyphenylene ether)
It calculated | required in polystyrene conversion by the gel permeation chromatography (GPC method).

Apparatus: Waters2690 (manufactured by Waters)
Detector: Differential refractometer RI (Waters 2410)
Column: TSK-gel-GMH-XL, 2 (manufactured by Tosoh Corporation)
Solvent: THF
Temperature: 38 ° C
E. IV: Intrinsic viscosity (polyester)
Measurement was performed at 25 ° C. using orthochlorophenol as a solvent.
F. Kneadability When the flame retardant is kneaded with a biaxial extruder, if the chip surface is not rough, the kneadability is good, ◎, if there is a slight roughness, ○, if there is a noticeable roughness, ×, ◎, ○ is preferable.
G. Combustibility Evaluation was made based on self-extinguishing properties, carbide content, and non-drip properties when a combustion test was performed according to JIS L1091 D method (1992). In all cases, ◎, ○, Δ, and X are preferred from the highest effect, and ◎ and ○ are preferred.
H. Comprehensive evaluation In kneadability and combustibility, x indicates that there are 2 or more, x indicates that there is 1 or more or x, Δ indicates that there are 3 or more, and A indicates that there are 3 or more. ◎ and ○ are preferable.

Synthesis example 1
DOW CORNING (R) 217 FLAKE RESIN (Toray Dow Corning Co., Ltd.) 100 g of silicone resin whose organic groups are all phenyl groups in a flask with a stirrer, 1.01 g of triphenylphosphine oxide (Wako Pure Chemical Industries, Ltd.) as a catalyst Then, 35.8 g of 3-methyl-4-isopropylphenol (M-Commerce Co., Ltd.) was added, the temperature was raised from room temperature to 120 ° C. at a rate of 4 ° C./min, and held for 2 hours. Stirring was started from around 60 ° C. when phenylsilsesquioxane and 3-methyl-4-isopropylphenol began to melt. Furthermore, after heating up to 230 degreeC with the temperature increase rate of 4 degree-C / min, it hold | maintained for 3 hours and performed the blocking reaction by the condensation reaction of silanol groups and 3-methyl-4- isopropylphenol of a silanol group. Thereafter, the pressure was reduced to 20 torr over 1 hour in order to remove unreacted 3-methyl-4-isopropylphenol while maintaining the temperature at 230 ° C. Cooling was performed to obtain organopolysiloxane (1) as a white solid. The weight average molecular weight (Mw) is 3900, and the glass transition temperature (Tg) is 89 ° C. Moreover, the composition formula of the organopolysiloxane resin calculated from 29Si NMR and 1H NMR is (C ₆ H ₅ ) Si (OR ′) _0.12 (OH) _0.04 O _1.42 , that is, m1 + m2 = 1, n = 0.2 + 0.04 = 0.16, and m1 + m2 + n = 1.16.

The obtained solid was further heat-treated in an oven at 300 ° C. in a thin film state for 5 hours and cooled to obtain a white solid organopolysiloxane resin (2). The organopolysiloxane resin (2) has a weight average molecular weight (Mw) of 4300 and a glass transition temperature (Tg) of 113 ° C. The composition formula is (C ₆ H ₅ ) Si (OR ′) _0.12 (OH) _0.03 O _1.425 , that is, m1 + m2 = 1, n = 0.12 + 0.03 = 0.15, m1 + m2 + n in Formula 1. = 1.15.

Example 1
IV (intrinsic viscosity): 0.66 polyethylene terephthalate (ethylene terephthalate unit: 100%) 79% by weight and molecular weight 2000 polyphenylene ether (Mitsubishi Gas Chemical OPE) 15% by weight, polyorganosiloxane synthesized in Synthesis Example 1 ( 2) Kneading using a twin screw extruder under the conditions of 6% by weight, L / D: 32.5, kneading temperature 280 ° C., screw rotation speed 300 rpm to obtain a resin composition, and then cutting into 3 mm square chips did. It was found that the chip surface was smooth, the dispersibility of the flame retardant was good, and the kneadability was excellent. The obtained chip was dried in a vacuum dryer at 150 ° C. for 12 hours and 2 Torr, and then a spinning temperature of 290 ° C., a spinning speed of 1500 m / min, a nozzle diameter of 0.23 mm, a hole depth of 0.15 mm and a hole number of 24. When spinning was performed under the condition of a discharge rate of 40 g / min and unstretched was obtained, no increase in the filtration pressure was observed, resulting in excellent production stability. Subsequently, using a drawing machine, drawing was performed at a drawing ratio such that the fineness of the drawn yarn was 85 dtex-24 filaments under the conditions of a processing speed of 400 m / min, a drawing temperature of 90 ° C., and a set temperature of 130 ° C. to obtain a drawn yarn. Thereafter, a fiber structure of a knitted fabric is produced from the obtained drawn yarn with a cylindrical knitting machine, and sodium carbonate 0.2 g / L, surfactant 0.2 g / L (Gran-up US20, manufactured by Sanyo Chemical Industries, Ltd.), treatment Scouring was carried out at a temperature / hour of 60 ° C./30 minutes, and a combustion test was conducted.
As a result, self-extinguishing properties, carbide content, and non-drip properties were all good. The results are shown in Table 1.

Example 2
IV (intrinsic viscosity): 0.66 polyethylene terephthalate (ethylene terephthalate unit: 100%) 83.6% by weight and molecular weight 2000 polyphenylene ether (Mitsubishi Gas Chemical OPE) 10% by weight, polyorgano synthesized in Synthesis Example 1 Kneading and spinning were performed in the same manner as in Example 1 using 6% by weight of siloxane (2) and 0.4% by weight of potassium perfluorobutanesulfonate. It was found that the dispersibility of the flame retardant is good and the kneadability is excellent. As a result of the combustion test, the self-extinguishing property, the carbide content, and the non-drip property were good. The results are shown in Table 1.

Example 3
80% by weight of polyethylene terephthalate copolymerized with 4% by mole of bisphenol A (96% by mole of ethylene terephthalate units), 10% by weight of polyphenylene ether (Mitsubishi Gas Chemical OPE) having a molecular weight of 2000, polyorganosiloxane synthesized in Synthesis Example 1 (1 ) Kneading and spinning were carried out in the same manner as in Example 1 using 7% by weight and 3% by weight of zinc borate. It was found that the dispersibility of the flame retardant was good. As a result of the combustion test, the self-extinguishing property, the carbide content, and the non-drip property were good. The results are shown in Table 1.

Example 4
IV (intrinsic viscosity): 0.66 polyethylene terephthalate (ethylene terephthalate unit: 100%) 78% by weight and polyphenylene ether (Mitsubishi Gas Chemical OPE-2Gy) 15% by weight substituted with glycidyl ether at the end of molecular weight 750, Kneading and spinning were carried out in the same manner as in Example 1 using 8% by weight of the polyorganosiloxane (2) synthesized in Synthesis Example 1 and 4% by weight of magnesium borate. It was found that the dispersibility of the flame retardant was good. As a result of the combustion test, the self-extinguishing property, the carbide content, and the non-drip property were good. The results are shown in Table 1.

Example 5
Polyphenylene ether (Mitsubishi Gas Chemical OPE-2St) having 78.4% by weight of polyethylene terephthalate (ethylene terephthalate unit: 94 mol%) substituted with 6 mol% of sodium sulfoisophthalate (SSIA) and 2200 molecular weight substituted with styrene. 10% by weight, 6% by weight of the polyorganosiloxane (2) synthesized in Synthesis Example 1 and 0.6% by weight of sodium p-toluenesulfonate were kneaded and spun in the same manner as in Example 1. It was found that the dispersibility of the flame retardant is good and the kneadability is excellent. As a result of the combustion test, the self-extinguishing property, the carbide content, and the non-drip property were good. The results are shown in Table 1.

Example 6
IV (intrinsic viscosity): 0.66 polyethylene terephthalate (ethylene terephthalate unit: 100%) 78% by weight, molecular weight 1000 polyphenylene ether (Mitsubishi Gas Chemical OPE) 12% by weight, polyorganosiloxane synthesized in Synthesis Example 1 ( 1) Kneading and spinning were performed in the same manner as in Example 1 using 5% by weight and 5% by weight of magnesium borate. It was found that the dispersibility of the flame retardant is good and the kneadability is excellent. As a result of the combustion test, the self-extinguishing property, the carbide content, and the non-drip property were good. The results are shown in Table 1.

Comparative Example 1
Kneading was carried out in the same manner as in Example 1 except that polyphenylene ether having a molecular weight of 44000 (IUPIACE XPY100L manufactured by Mitsubishi Engineering Plastics) was used instead of the polyphenylene ether having a molecular weight of 2000. It was found that the surface of the obtained chip was rough and the dispersibility of the flame retardant was very poor. In addition, since the yarn production evaluation cannot be performed, the overall evaluation is x. The results are shown in Table 2.

Comparative Example 2
The examination was conducted without using organopolysiloxane. Although kneadability was good, the result was inferior in flame retardancy. The results are shown in Table 2.

Comparative Example 3
The examination was conducted without using polyphenylene ether. Although the kneadability was good, the flame retardancy was not sufficient.

Comparative Example 4
Instead of organopolysiloxane, dimethyl silicone oil (Me2SiO: SH200 1000CS manufactured by Toray Dow Corning Co., Ltd.) was used. The kneadability was at a level with no problem, but the result was inferior in flame retardancy. The results are shown in Table 2.

Comparative Example 5
When a polyphenylene ether having a molecular weight of 44000 (IUPIAC XPY100L manufactured by Mitsubishi Engineering Plastics) and styrene were kneaded with an extruder so as to have a weight ratio of 2 to 3, a uniform polymer was obtained.
The polymer was kneaded in the same manner as in Example 1 using 25% by weight. The kneadability was at a level with no problem, but the result was inferior in flame retardancy. The results are shown in Table 2.

Claims (5)

  A flame retardant polyester resin composition comprising at least 5 to 30% by weight of polyphenylene ether having a molecular weight of 500 to 10,000 and 0.5 to 20% by weight of polyorganosiloxane. The flame-retardant polyester resin composition according to claim 1, wherein the polyorganosiloxane is represented by the following general formula.
(C ₆ H ₅ ) _m1 R _m2 SiX _n O _{(4-m1-m2-n) / 2} (1)
[In the formula, R is a monovalent organic group excluding a hydrogen atom or a phenyl group, X is an OH group or a hydrolyzable group, and m1, m2, and n are
0.3 ≦ m1 ≦ 1.8,
0 ≦ m2 ≦ 1.5,
1.0 ≦ m1 + m2 <2.0,
0.2 ≦ m1 / (m1 + m2) ≦ 1.0,
0 ≦ n ≦ 1.5
A number satisfying the range of
1.0 ≦ m1 + m2 + n ≦ 3.0
It is a number that satisfies   The flame retardant polyester resin composition according to claim 1 or 2, which contains 0.01 to 3% by weight of an organic alkali metal sulfonate and / or an organic alkaline earth metal sulfonate.   The flame-retardant polyester resin composition according to any one of claims 1 to 3, comprising 1 to 15% by weight of a boric acid metal salt.   A fiber structure comprising the flame retardant polyester resin composition according to any one of claims 1 to 4.